JP3289193B2 - Amine-bound resin and antifouling paint - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a hydrolysis-type resin useful as a vehicle resin of an antifouling paint, and an antifouling paint composition containing the resin.

An antifouling paint using a trialkyltin polymer compound as a vehicle is known. This antifouling paint is excellent in that the elution amount of the antifouling agent is suppressed to a minimum level for maintaining the antifouling property, and a certain amount is eluted for a long period of time. In this paint, the trialkyltin polymer compound used as a vehicle is hydrolyzed in a slightly alkaline atmosphere of seawater to release the tin compound, and the vehicle becomes water-soluble and the coating film is consumed.
As a result, the unevenness of the coating film becomes smooth, which reduces the seawater frictional resistance of the ship and contributes to a reduction in fuel cost.

The vehicle resin of the self-polishing paint is, for example, a copolymer of tributyltin (meth) acrylate. However, due to concerns about the effect of trialkyltin on ecosystems, development of a self-polishing vehicle resin for antifouling paints instead of a trialkyltin polymer compound is desired.

Many of the vehicle resins for self-polishing antifouling paints proposed so far release metal compounds or ions. Recently, the present inventors have found that primary amines, such as aniline and its nucleus-substituted product, also have an antifouling effect on attached organisms.

Accordingly, an object of the present invention is to provide a new type of antifouling paint vehicle resin, which releases a primary amine having an antifouling effect in a controlled manner by hydrolysis, while the remaining coating film is water-soluble and gradually consumed. To provide.

DISCLOSURE OF THE INVENTION It is well known in the field of organic chemistry that primary amines react with aldehydes to form Schiff bases and ketones to form ketimines.

The present invention utilizes these reactions to attach the primary amine to the vehicle resin in a hydrolyzable form.

Therefore, the present invention relates to a method in which a primary amine is bonded to a carbonyl group of a vinyl polymer having a carbonyl group-containing pendant group by a condensation reaction, or a primary amine is bonded to a carbonyl group-containing monomer by a similar reaction. A vehicle resin for an antifouling paint comprising a vinyl polymer, which is obtained by copolymerizing the obtained monomer with another copolymerizable monomer.

The present invention also provides an underwater antifouling paint using a vinyl polymer having a primary amine bonded thereto as a vehicle resin.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to obtain the primary amine-linked vinyl polymers of the present invention, the primary amine must be started from a monomer having an aldehyde or ketone group attached after or before polymerization. . Typical examples of monomers having an aldehyde group include acrolein, methacrolein, crotonaldehyde, cinnamaldehyde, and 4-vinylbenzaldehyde. Low boiling, irritating and active aldehydes, such as acrolein, are used in the form of cyclic acetals with acetal, for example ethylene glycol or 1,3-propanediol, to avoid side reactions and to facilitate handling, The aldehyde group may be regenerated by hydrolysis before the reaction with the primary amine. Examples of the monomer having a ketone group include N- (2-acetyl-1,1-dimethylethyl)
Acrylamide (also known as diacetone acrylamide) and the like.

Examples of monomers that can be copolymerized with the aldehyde group or ketone group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate,
Alkyl (meth) acrylates such as t-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; styrene, α-methylstyrene, vinyltoluene, (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, propionic acid There are other monomers such as vinyl, vinyl chloride. It may contain a small proportion of hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. The polymerization can be performed by a conventional method using a solution polymerization method.

The condensation reaction between the aldehyde group or the ketone group and the primary amine may be performed after the polymerization, or may be performed at the monomer stage and then the polymerization. Primary amines that can be used for this purpose include aniline, toluidine, xylidine, p
-N-hexylaniline, pn-octylaniline,
an aniline such as p-nonylaniline and p-dodecylaniline and an aromatic primary amine containing a nuclear substituent thereof, an alicyclic primary amine such as cyclohexylamine, hexylamine, octylamine, decylamine, laurylamine,
Examples thereof include aliphatic amines having 6 or more carbon atoms, such as stearylamine and oleylamine. In particular, aniline and its alkyl-substituted product, alkylamine and alkenylamine having 8 to 20 carbon atoms are preferable. The reaction can be easily carried out under the condition of removing by-product water and the like out of the system.

The polymer preferably has a number average molecular weight of 2,000 to 100,000, especially 5,000 to 40,000. This is necessary to maintain an appropriate balance between film forming properties, workability and dissolution rate. The polymer also contains 0.01 to 1.5 mol / 100 g of primary amine bound to an aldehyde or ketone group, especially 0.1 to 1.
Preferably, it is contained at a concentration of 0 mol / 100 g.

The above-mentioned primary amines have an antifouling effect even when added to the paint as an independent component. In that case benzaldehyde, p
Aldehydes such as ethylbenzaldehyde may be added simultaneously as independent components or in the form of Schiff bases with primary amines.

The thus obtained resin having a primary amine bonded thereto is prepared into a self-polishing antifouling paint composition by adding conventional additives including an antifouling agent.

The antifouling paint composition of the present invention can contain the following conventional components added to the antifouling paint.

(1) Antifouling agent: metal powder or flakes such as copper, zinc and nickel;
Oxides, hydroxides, halides and other salts of copper, zinc and the like, especially cuprous oxide and copper rhodan; fungicidal organic compounds such as metal carboxylates such as copper naphthenate and copper stearate; zinc dimethyldithiocarbamate , Bisdimethyldithiocarbamoyl zinc, ethylenebisdithiocarbamate and other metals (Na, K, Zn, Pb, Cu, Fe, Ni, Mg, S
e) dithiocarbamates; thiuram disulfides such as tetramethylthiuram disulfide; phthalylsulfatithiazole, sulfaethidol, sulfanilide pyridine, sulfomethoxine, N, N'-dimethyl-
Sulfamides such as N′-phenyl-N-fluorodichloromethylthiosulfamide; pyrroles such as gliosin, fenthisol, and polycide; imidazoles; thioxanes such as terazole, asterol, and mylon;
Thiozansons; imides such as nicarbazine, 3,4,5-tribromosalicylanilide, N-trichloromethylmercaptophthalimide, 3,5-dinitrobenzamide, 2,4,6-trichloromaleimide, N-fluorodichloromethylthiophthalimide and the like; Amides; 2-methylthio-4
-T-butylamino-6-cyclopropylamino-s-
Triazine, 2,4,5,6-tetrachlorophthalonitrile,
N, N'-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-3- (2H) isothiazoline, 2-
Sulfur-containing or halogen-containing organic compounds such as pyridinethiol-1-oxide zinc salt, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 3-iodo-2-propylbutylcarbamate and diiodomethylparatolylsulfone There are known antifouling agents such as compounds, pesticides, medicines, and fungicides.

(2) Plasticizer: phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, and dicyclohexyl phthalate;
Aliphatic dibasic acid ester plasticizers such as diisobutyl adipate and dibutyl sebacate; glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate plasticizers such as tricresyl phosphate and trichloroethyl phosphate Epoxy plasticizers such as epoxidized soybean oil and octyl epoxy stearate; organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate; and trioctyl trimellitate and triacetylene.

(3) Paint consumption modifier: chlorinated paraffin, polyvinyl ether, polypropylene sebacate, partially hydrogenated terphenyl, polyvinyl acetate, poly (meth) acrylate, polyether polyol, alkyd resin, polyester resin, poly Examples include vinyl chloride, silicone oil, wax, petrolatum, and liquid paraffin.

(4) Pigments: extenders such as precipitated barium sulfate, talc, clay, chalk, silica white, alumina white, bentonite; titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite, red iron, chrome There are coloring pigments such as yellow, phthalocyanine green, phthalocyanine blue, and quinacridone.

(5) Solvents: hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, peptane, cyclohexane, white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethers such as butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; ethyl isobutyl ketone; Ketones such as methyl isobutyl ketone; n- Ethanol, and the like alcohols such as propyl alcohol.

(6) Other additives: Organic monobasic acids such as rosin, monobutyl phthalate and monooctyl succinate, camphor, castor oil and the like.

The composition of the present invention can be prepared by a method known per se in the technical field of paint production. For the preparation, a known machine such as a ball mill, a pebble mill, a roll mill, and a sand grind mill can be used.

When the antifouling paint of the present invention is used as an antifouling paint for ships, fishing nets, marine structures, etc., the coating film or film is gradually hydrolyzed and eluted in an alkaline atmosphere such as seawater. In addition, when hydrolyzed in an alkaline atmosphere, the resin is not decomposed into small segments and eluted at once, but a hydrophilic group is generated in the side chain, and the resin elutes only when the concentration reaches a certain critical value. Take. Therefore, when used as a vehicle for ship bottom paint, it is possible to give a coating film having very good properties, which has a feature that the antifouling period can be controlled over a long period of time. Accordingly, the antifouling paint of the present invention is applicable to ships such as tankers, ferries, fishing boats, steel boats, wooden boats, FRs.
Useful for underwater structures, fish nets, water pipes, etc., such as P-ships.

In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are based on weight.

Production of Vehicle Resin Production Example 1 95 parts of xylene and 13 parts of cinnamaldehyde were added to a flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, and the mixture was heated at 90 ° C
To keep. To this solution, a mixture of 67 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 1.5 parts of 2,2′-azobisisobutyronitrile was added dropwise over 4 hours. After 30 minutes, 5 parts of n-butanol and 2,2 ′ A mixture of 0.3 parts of azobisisobutyronitrile was added dropwise over 30 minutes, and the same temperature was maintained for 90 minutes to obtain Varnish A. Aldehyde concentration 0.05mol / 10
0g Production Example 2 95 parts of xylene and 14 parts of methacrolein are added to a flask similar to that of Production Example 1, and kept at 80 ° C. 66 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 2,
A mixture of 1.5 parts of 2'-azobisisobutyronitrile was added dropwise over 4 hours, and 30 minutes later, 5 parts of n-butanol and 2,2 '
-A mixture of 0.3 parts of azobisisobutyronitrile was added dropwise over 30 minutes, and the mixture was kept at the same temperature for 90 minutes to obtain Varnish B.
Aldehyde concentration: 0.1 mol / 100 g Preparation Example 3 To a flask similar to Preparation Example 1, 95 parts of xylene and 34 parts of diacetone acrylamide are added and kept at 80 ° C. A mixture of 46 parts of methyl methacrylate, 20 parts of n-butyl methacrylate and 1.5 parts of 2,2'-azobisisobutyronitrile was added dropwise to this solution over 4 hours, and 30 minutes later, n-butanol 5
Parts, a mixture of 0.3 parts of 2,2′-azobisisobutyronitrile
Drop in 0 minutes, keep at the same temperature for another 90 minutes
I got Ketone group concentration: 0.1 mol / 100 g Preparation Example 4 To a flask similar to Preparation Example 1, 145 parts of xylene and 35 parts of crotonaldehyde are added and kept at 0 ° C. To this solution was added 47 parts of aniline, kept for 2 hours, and then heated to 40 ° C.
The temperature was maintained for the same time. Next, the produced water was removed under a reduced pressure of about 250 Pa to obtain a monomer having a primary amine bonded thereto.

Production Example 5 35 parts of methacrolein are added to a flask similar to that of Production Example 1 and kept at 0 ° C. To this was added 100 parts of p-octylaniline, and the mixture was kept for 2 hours, then heated to 40 ° C. and kept for 2 hours. Next, the produced water was removed under a reduced pressure of about 250 Pa to obtain a monomer having a primary amine bonded thereto.

Production Example 6 To a flask similar to that of Production Example 1, 95 parts of xylene and 20 parts of 2-vinyl-1,3-dioxolane (acetal of acrolein and ethylene glycol) are added, and the mixture is kept at 80 ° C. 46 parts of methyl methacrylate, 20 parts of styrene, n-
A mixture of 14 parts of butyl methacrylate and 1.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 5 hours, and after 30 minutes, a mixture of 5 parts of xylene and 0.2 part of 2,2′-azobisbutyronitrile was added to 30 parts. After the dropping, the solution was kept warm for 90 minutes.
Next, 200 parts of 1N hydrochloric acid was added, the mixture was stirred at room temperature for 2 hours, the aqueous phase was removed, and the mixture was washed twice with deionized water. After removing water remaining with 20 parts of xylene under a reduced pressure of 150 Pa, 20 parts of xylene was added again to obtain Varnish D. Aldehyde concentration 0.1 mol / 100 g Production Example 7 In a flask similar to Production Example 1, 95 parts of xylene, 35 parts of 2-vinyl-1,3-dioxane (acetal of acrolein and 1,3-propanediol), and 25 parts of vinyl acetate Plus 90
Keep at ° C. To this solution, 30 parts of methyl methacrylate, 2-
A mixture of 10 parts of ethylhexyl acrylate and 1.5 parts of 2,2′-azobisisobutyronitrile was added dropwise over 5 hours.
0 minutes later, a mixed solution of 5 parts of xylene and 0.2 parts of 2,2'-azobisisobutyronitrile was added dropwise over 30 minutes, and the mixture was kept warm for 90 minutes after the addition. Next, 300 parts of 1N hydrochloric acid was added, the mixture was stirred at room temperature for 2 hours, the aqueous phase was removed, and the mixture was washed twice with deionized water. The remaining water was removed together with 20 parts of xylene under a reduced pressure of 150 Pa, and 20 parts of xylene was added again to obtain a varnish E. Aldehyde concentration 0.
15 mol / 100 g Production Example 8 95 parts of xylene was added to the same flask as in Production Example 1,
Keep at 0 ° C. To this, 55 parts of the monomer of Production Example 4, 35 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 2,2 ′
-A mixture of 1.3 parts of azobisisobutyronitrile was added dropwise over 4 hours. After 30 minutes, a mixture of 5 parts of xylene and 0.5 part of 2,2'-azobisisobutyronitrile was added dropwise over 30 minutes. The mixture was kept warm for a minute to obtain Varnish F.

Production Example 9 To a flask similar to that of Production Example 1, xylene 95 was added, and 100
Keep at ° C. To this, 55 parts of the monomer of Production Example 5, 45 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 1.
A mixture of 3 parts was added dropwise over 4 hours, and after 30 minutes, a mixture of 5 parts of xylene and 0.2 parts of 2,2'-azobisisobutyronitrile was added dropwise over 30 minutes. Obtained.

Production Example 10 100 parts of varnish A and 12 parts of p-decylaniline were added to a flask equipped with a stirrer, a nitrogen inlet tube, and a decanter. This solution was refluxed at about 130 ° C., and the reaction was carried out for 3 hours while distilling off generated water, to obtain a varnish H.

Production Example 11 As in Production Example 10, varnish I was obtained by reacting 100 parts of varnish B with 9 parts of aniline.

Production Example 12 As in Production Example 10, varnish B100 parts and dodecylamine
By reacting with 17 parts, Varnish J was obtained.

Production Example 13 As in Production Example 10, varnish K was obtained by reacting 100 parts of varnish E with 43 parts of p-nonylaniline.

Production Example 14 In the same manner as in Production Example 10, varnish L was obtained by reacting 100 parts of varnish C with 23 parts of p-decylaniline.

Production Example 15 Varnish D100 parts and oleylamine 27 as in Production Example 10
The parts were reacted to obtain Varnish M.

Production Example 16 Varnish N was obtained in the same manner as in Production Example 9 except that 75 parts of 4-vinylbenzylideneaniline and 25 parts of methyl methacrylate were used as the monomer mixture.

Production Example 17 85 parts of N- (4-vinylbenzylidene) -4-n-octylaniline as a monomer mixture in Production Example 9;
Varnish O was obtained in the same manner except that 15 parts of methyl methacrylate was used.

Production Example 18 Varnish P was obtained in the same manner as in Production Example 9 except that 85 parts of an adduct of diacetone acrylamide and laurylamine and 15 parts of methyl methacrylate were used as the monomer mixture.

Production Example 19 Varnish Q was obtained in the same manner as in Production Example 9 except that 80 parts of N- (4-vinylbenzylidene) laurylamine and 20 parts of methyl methacrylate were used as the monomer mixture.

Production of Paints Examples 1 to 30 and Comparative Examples 1 to 4 Each component was dispersed with a disper according to the formulations shown in Tables 1 to 4 to produce paints.

Anti-fouling test The paints of Examples 1 to 30 and Comparative Examples 1 to 4 were applied to a sand blasted 9 × 28 cm steel plate which had been previously coated with a tar epoxy paint and which had been subjected to rust prevention treatment. Thus, a test plate was prepared.

Separately, varnishes F to Q were applied to a 9 × 28 cm polyvinyl chloride resin plate so as to have a dry film thickness of about 100 μm to prepare test plates.

These test plates were immersed in the sea at Nippon Paint Co., Ltd., Nippon Paint Co., Ltd. in Tamano City, Okayama Prefecture, and the antifouling property over time was evaluated based on the area (%) to which living organisms adhered. The results are shown in Tables 5 and 6.

Paint film wear degree test The paints and varnishes F to Q of the examples and the comparative examples have a diameter of
Apply to a 35cm acrylic resin disc to a dry film thickness of about 100μm, and in seawater (water temperature 18 ~ 23 ℃) at a peripheral speed of 25 knots
It was rotated continuously for 12 months, and the difference from the initial film thickness over time was measured as the degree of consumption of the coating film. The results are shown in Tables 7 and 8.

DISCUSSION The antifouling paint resin and antifouling paint of the present invention exhibited performance comparable to the self-polishing antifouling paint of Comparative Example 4 using an organotin polymer in antifouling properties and self-polishing properties.

Continuation of the front page (56) References JP-A-57-4905 (JP, A) JP-A-58-177904 (JP, A) JP-A-7-138504 (JP, A) JP-A-1-131286 (JP) , A) JP-A-1-131285 (JP, A) JP-A-4-1277 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 5/16 C08F 8/32 C08F 212/14 C08F 226/02

Claims (14)

(57) [Claims] 1. A self-polishing antifouling paint comprising an antifouling agent and a vinyl polymer having a plurality of pendant groups to which a primary amine is bonded as a vehicle resin, wherein the primary amine is pendant. A self-polishing antifouling paint bonded to the pendant group by a dehydration condensation reaction with a carbonyl group on the group. 2. The self-polishing antifouling paint according to claim 1, wherein the primary amine is an aromatic primary amine. 3. The aromatic primary amine is aniline, toluidine, xylidine, pn-hexylaniline, pn-
The self-polishing antifouling paint according to claim 2, which is octylaniline, p-nonylaniline, or p-dodecylaniline. 4. The self-polishing antifouling paint according to claim 1, wherein the primary amine is an aliphatic or alicyclic primary amine having 6 or more carbon atoms. 5. The self-polishing antifouling paint according to claim 4, wherein the aliphatic or alicyclic primary amine is hexylamine, octylamine, decylamine, laurylamine, stearylamine, oleylamine or cyclohexylamine. 6. A vinyl polymer having a plurality of pendant groups to which a primary amine is bonded is produced by reacting a primary amine with a vinyl polymer having a plurality of carbonyl-containing pendant groups. Item 1. A self-polishing antifouling paint according to item 1. 7. The vinyl polymer having a plurality of carbonyl group-containing pendant groups is a copolymer of a monomer having an aldehyde group or a ketone group and a vinyl monomer copolymerizable therewith. Self-polishing antifouling paint. 8. The monomer having an aldehyde group or a ketone group is acrolein, methacrolein, crotonaldehyde, cinnamaldehyde, 4-vinylbenzaldehyde, or N- (2-acetyl-1,1-dimethylethyl) acrylamide. The self-polishing antifouling paint according to claim 7. 9. A vinyl copolymer having a plurality of pendant groups to which a primary amine is bonded, a dehydration condensation product between a carbonyl group-containing monomer and a primary amine, and a vinyl monomer copolymerizable therewith. 2. The self-polishing antifouling paint according to claim 1, which is produced by copolymerization with the following. 10. The self-polishing antifouling paint according to claim 9, wherein the dehydration condensation product is a Schiff base of an aldehyde group-containing monomer and a primary amine or a ketimine of a ketone group-containing monomer and a primary amine. 11. The aldehyde group or ketone group-containing monomer is acrolein, methacrolein, crotonaldehyde, cinnamaldehyde, 4-vinylbenzaldehyde, or N- (2-acetyl-1,1-dimethylethyl) acrylamide. Item 10. A self-polishing antifouling paint according to item 10. 12. The self-polishing antifouling paint according to claim 1, wherein said vinyl polymer having a plurality of pendant groups bonded to a primary amine has a number average molecular weight of 2,000 to 100,000. 13. A vinyl polymer having a plurality of pendant groups to which a primary amine is bonded, wherein the vinyl polymer has a content of 0.01 to 1.5 mol / 100.
2. The composition of claim 1 having an amine-bonded carbonyl group concentration of g.
Self-polishing antifouling paint. 14. The self-polishing antifouling paint according to claim 1, wherein the antifouling agent is cuprous oxide or copper rhodan.